Carbonates of ether and hydroxy substituted fatty nitriles

ABSTRACT

ETHER CARBONATE DINITRILES OF THE FORMULA: ((H-(CH2)N-)2(-Z-)(-(CH2)M-C*N)2 WHERE Z IS -CH(-O-R)-CH(-)-O-CO-O-CH(-)-CH(-O-R)-,   -CH(-CH(-)(-O-R))-O-CO-O-CH(-)(-CH(-)(-O-R)) AND/OR   -CH(-O-R)-CH(-)-O-CO-O-CH(-)-CH(-)(-O-R) WHERE N IS 4 TO 19, M IS 0 TO 15, THE SUM OF N AND M IS 13 TO 19 AND R IS A MONOVALENT ORGANIC RADICAL. DIAMINES AND DIISOCYANATES DERIVED THEREFROM WITH THE LATTER BEING USEFUL FOR PREPARING POLYMERS.

United States Patent ABSTRACT oF THE DISCLOSURE Ether carbonatedinitriles of the formula:

where Z is where n is 4 to 19, m is O to 15, the sum of n and m is 13 to19 and R is a monovalent organic radical. Diamines and diisocyanatesderived therefrom with the latter being useful for preparing polymers.

The present invention relates to new ether carbonate dinitriles. Moreparticularly, it relates to such ether carbonate dinitriles preparedfrom certain ether and hydroxy substituted fatty nitriles and phosgene.

The new dinitriles of the present invention have the structural formula:

where n is 4 to 19, m is 0 to 15, the sum of n and m is 13 to 19, and Ris a monovalent organic radical. The sum of the whole integers m and nis preferably 15. R is preferably a monovalent hydrocarbon radical of 1to about 20 carbon atoms.

Our new ether carbonate dinitriles are useful as intermediates (via thenitrile groups) in the preparation of diacids, diesters, diamines andthe like. The diamines, for example, are useful for preparingdiisocyanates which in turn can be reacted with a variety of organiccompounds'containing' two or more active hydrogens to yield polymershaving utility as coatings, moldings and the like. r

The ether carbonate dinitriles of our invention can be prepared by thereaction of phosgene with an ether and hydroxy substituted fattynitrile. The starting ether and hydroxy substitutedfatty nitriles areprepared by the re- 3,647,853 Patented Mar. 7, 1972 action of amonohydroxy compound with an epoxy substituted fatty nitrile. The epoxysubstituted fatty nitriles can be prepared in a number of known waysfrom monoethylenically unsaturated fatty nitriles of 16 to 22 carbonatoms. The preparation of the nitriles from the corresponding fattyacids and ammonia is also well known. This preparation and theconditions useful in the same are set forth in Fatty Acids And TheirDerivatives by A. W. Ralston, 1948, pp. 620 625 (John Wiley & Sons,Inc). The useful monoethylenically unsaturated aliphatic monobasiccarboxylic acids which can be converted to the mono-nitriles and then tothe starting epoxy substituted mono-nitriles can be represented by thefollowing: 9-hexadecenoic (palmitoleic), 7-hexadecenoic, 2-hexadecenoic, 2-heptadecenoic, 2-octadecen0ic, 3-octadecenoic,4-octadecenoic, 5-octadecenoic, 6-octadecenoic (pertrolselinic),7-octadecenoic, 8-octadecenoic, 9-octadecenoic (oleic, elaidic), lO-octadecenoic, ll-octadecenoic (vaccenic), 12-octadecenoic,2-nonadecenoic, 9-eicosenoic (gadoleic), ll-eicosenoic, 13-docosenoic(erucic), lldocosenoic (cetoleic) and the like. The oxidation of themono-nitriles to the epoxy substituted nitriles is readily accomplishedwith mild oxidizing agents, preferably peracetic acid. The epoxysubstituted nitriles can also be prepared according to the procedure ofUS. Pat. 2,756,242.

The epoxy substituted fatty nitrile is then converted to an ether andhydroxy substituted nitrile by reaction with a monohydroxy compound.Such reaction (or etherification) is preferably carried out in thepresence of an acid catalyst. Sulfuric acid is one preferred catalyst. Awide variety of monohydroxy compounds can be utilized. Representative ofsuch are: aliphatic alcohols including methanol, ethanol, propanol,isopropanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol,nonanol, decanol, dodecanol, hexadecanol, octadecanol, and the like;phenols such as phenol, p-nonyl phenol, o-cresol, other alkylsubstituted phenols, and the like; cycloaliphatic alcohols such ascyclohexanol, and alkyl substituted cyclohexanols; and aryl substitutedaliphatic alcohols such as benzyl alcohol, and alkyl substituted benzylalcohols. The alkyl substituents on the various classes of alcohols andphenols can be branched or straight chained and preferably contain from1 to 12 carbon atoms. The monohydroxy compounds can also contain inertsubstituents such as Cl, nitro and the like but it is preferred that theresulting R group be unsubstituted hydrocarbon. The preferredmonohydroxy compounds are the saturated aliphatic alcohols of l to about18 carbon atoms.

The described ether and hydroxy substituted fatty nitriles are thenreacted with phosgene to produce the new ether carbonate dinitriles ofthe present invention. Such phosgenation can be carried out bydissolving the ether and hydroxy substituted fatty nitriles in anorganic solvent such as toluene, benzene, pyridine (also an acidacceptor) and the like or mixtures thereof followed by the slow additionof phosgene gas, preferably at temperatures below about 25 C.i.e. 0 to25 C.

The following examples are illustrative of the invention without beinglimiting.

EXAMPLE I To a solution of 664 g. of a mixture of approximately equalparts of 9-met'hoxy-10-hydroxystearonitrile and 10-methoxy-9-hydroxystearonitrile in 700 g. dry toluene and 240 g. drypyridine was added 131 g. of phosgene gas over a period of four hourswhile maintaining the temperature at 5-10 C. The reaction mixture wasallowed to warm to 20 C. over a one hour period and then diluted withwater. The resulting top layer was separated, washed with saturated saltwater, and stripped free of toluene on a rotary evaporator, leaving 693g. of crude product which was filtered to remove a small amount of whitesolid. The

resulting product analyzed 4.35% nitrogen (theoretical 4.32%) and theinfrared spectrum thereof showed absorption maxima at 4.46 (nitrileCEN), 5.74 t (carbonate C=O), 7.89 (carbonate C-O) and 9.09 11. (etherC-O). The product comprised a mixture of position isomers having theformulae:

These position isomers can be separated (as well as the isomers of theexamples to follow) such as by chromatography. However, there isordinarily no reason to do so since the compounds are functionallyequivalent.

EXAMPLE 11 Example I is essentially repeated using a mixture of 9-octyloxy hydroxystearonitrile and 10-octyloxy-9-hydroxystearonitrile.The resulting product corresponds to that of Example 1 except that themethoxy groups are replaced by octyloxy group (OCH (CH CH EXAMPLE IIIExample I is essentially repeated using a mixture of 9- cetyloxy 10hydroxystearonitrile and 10-cetyloxy-9-hydroxystearonitrile. Theresulting product corresponds to that of Example I except that themethoxy groups are replaced by cetyloxy groups (0CH (CH CH EXAMPLE IVExample I is essentially repeated using a mixture of 9- phenoxy 1Ohydroxystearonitrile and 10-phenoxy-9-hydroxystearonitrile. Theresulting product corresponds to that of Example I except that themethoxy groups are replaced by phenoxy groups 4 temperature. Thereaction is preferably carried out in an organic solvent such astolueneor xylene.

The utility of our new dinitriles is accordingly illustrated by thefollowing description.

The following examples serve to illustrate the preparation of thediamines without being limiting.

EXAMPLE A A mixture of 160 g. of the ether carbonate dinitrile asprepared in Example I, 160 g. of methanol, 24.0 g. Raney active cobaltcatalyst and 150 ml. liquid ammonia was heated in a stirred autoclavefor 4 hours at -150 C. under hydrogen at 810-1130 p.s.i. The reactionmixture was then cooled to room temperature, filtered and stripped freeof solvent on a rotary evaporator. The resulting crude product (157.0g.) was a dark redbrown liquid. The above procedure was essentiallyrepeated three more times giving a total of 552 g. of crude product withan amine number of 168. This combined .crudeproduct was purified bydistillation through a falling-fihn molecular still to give a yellowliquid with an amine number of 169 (theoretical 171). The productcomprised a mixture of position isomers having the formulae:

These position isomers can be separated (as well as the isomers of theexamples to follow) such as by chromatography. However, there isordinarily no reason' to do so since the compounds are functionallyequivalent.

responds to that of Example A except that the methoxy groups arereplaced by cetyloxy groups Example A is essentially repeated using theether carbonate dinitrile of Example IV. The resulting product .and

corresponds to that of Example A except that the methoxy groups arereplaced by phenoxy groups The following examples serve to illustratethe preparation ofv the diisocyanates without being limiting.

EXAMPLE E To a solution of 318 g. phosgene in 800 ml. dry xylene wasadded a solution of 244 g. of the ether carbonate diamine as prepared"in Example A in 200 ml. dry xylene over a period of one hour. Duringthis time the reaction temperature increased to 30 C. The temperaturewas then increased to 115 C. in 2 /3 hours. Nitrogen gas was thenbubbled through the reaction mixture and the xylene distilled off to apot temperature of 175 C. at atmospheric pressure. The residue was thenheld at 175 C. for minutes under full vacuum of a water aspirator. Theresulting dark viscous liquid was distilled through a fallingfilm stillat a jackettemperature of 200 C. to give a yellow liquid. Analysis andinfrared spectrum showed that the product had a nitrogen content of 4.0%(theoretical 3.96% an NCO content of 11.4% (theoretical 11.9%) andabsorption maxima at 4.42/1. (NCO), 5.75 (carbonate 0 0), 7.92;].(carbonate CO) and 9.08 t (ether CO). It comprised a mixture of positionisomers of the formulae:

Ill

EXAMPLE F Example E is essentially repeated using the ether carbonatediamineof Example B. The resulting product corresponds to that ofExample E except that the methoxy groups are replaced by octyloxy groupsEXAMPLE G Example E is essentially repeated using the ether carbonate.diamineof Example. C. The resulting product corresponds to that ofExample E except that the methoxy groups are replaced by cetyloxy groupszl z) 14 )3 EXAMPLE H Example E is essentially repeated using the ethercarbonate diamine of Example D. The resulting product corresponds tothat of Example E except that the methoxy groups are replaced by phenoxygroups As indicated above the diisocyanates are particularly valuablefor the preparation of polymers by reaction with compounds bearing atleast two active hydrogen atoms as determined by the Zerewitinoffmethod. The Zerewitinolf test is described by Kohler in I. Am. Chem.Soc., 49, 3181 (1927). Such polymers are useful especially as coatingsfor a variety of substrates.

In general, the active hydrogen atoms of compounds reactive with thediisocyanates are attached to carbon, oxygen, nitrogen or sulfur atoms.Compounds containing the following groups will have active hydrogenatoms: primary amino, secondary amino, carboxyl, diazoamino, hydrazino,hydrazo, hydrazono, hydroxyamino, hydroxyl imido, imino, and mercapto.Most often these active hydrogen atoms are attached to oxygen, nitrogen,or sulfur atoms; thus they will be a part of groups such as -OH, SH, NH,-NH -CO H, CONH CONHR where R represents an organic radical, SO OH, SONH and --CSNH Examples of suitable types of compounds include water,hydrogen sulfide, ammonia, hydroxyl polyesters, polyhydric polyalkyleneethers, polyhydric polythioethers, polyacetals, aliphatic polyols,including alkane, alkene and alkyne diols, triols, tetrols and the like,aliphatic thiols including alkane, alkene and alkyne thios having two ormore -SH grouups; polyamines including both aromatic, aliphatic andheterocyclic diamines, triamines, tetramines and the like; as well asmixtures thereof. Of course, compounds which contain two or moredifferent groups within the above-defined classes may also be used suchas, for example, amino alcohols which contain an amino group and ahydroxyl group, amino alcohols which contain two amino groups and onehydroxyl group, aminoacids and the like. Further illustrative classesand specific organic compounds containing active hydrogen atoms usefulfor preparing polymers are described immediately hereinbelow.

Any suitable polyester may be used and may contain terminal hydroxylgroups, terminal carboxylic acid groups, amino groups or the like.Moreover, the polyester may be a polyester amide which was prepared bycondensing an amino alcohol containing both free amino groups and freehydroxyl groups with the other components used in the preparation ofpolyesters. The polyester may be prepared by reacting a polycarboxylicacid or hydroxy carboxylic acid with polyhydric alcohols. It is alsopossible to use a mixture of polyhydric alcohols and polyamines such asethylenediamine, polyethylenediamine, 1,4-butyl enediamine and the like.Amines such as bis-(2-aminoethyl)ether or amino carboxylic acids such asglycine, alanine, valine, phenylalanine, hydroxypyroline and the likemay also be used. The polyesters may contain hetero atoms in addition tothe ester groups including oxygen, sulfur nitrogen and the like in thechain. Moreover, the radicals making up the polyester may be eithersaturated or unsaturated and may contain double or triple bonds as wellas modifying radicals of saturated or unsatuurated fatty acids such asoleic acid or fatty alcohols such as oleyl alcohol and the like.

Any suitable polycarboxylic acid may be used in the preparation of thepolyesters such as, for. example, oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaicacid, sebacic acid, brassylic acid, maleic acid, fumaric acid,glutaconic acid, alpha-hydromuconic acid, beta-hydromuconic acid,alpha-butyl-alpha-ethyl-glutaric acid, alpha,beta-diethylsuccinic acid,isophthalic acid, terephthalic acid, hemimellitic acid, trimelliticacid, trimesic acid, mellophanic acid, prehnitic acid, pyromelliticacid, benzenepentacarboxylic acid, 1,4-cyclohexanedicarboxylic acid, andthe like. Any suitable polyhydric alcohol may be used in the preparationof the polyesters such as, for example, ethylene glycol, 1,3-propyleneglycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol,1,2-butylene glycol, 1,5- pentanediol, 1,4-pentanediol, 1,3-pentanediol,1,6-hexanediol, 1,7-heptanediol, glycerine, trimethylolpropane, 1,3,6-hexanetriol, triethanolamine, pentaerythritol, sorbitol and the like.

Any suitable polyhydric polyalkylene ether may be used as the activehydrogen containing compound such as, for example, the condensationproduct of an alkylene oxide or of an alkylene oxide With a polyhydricalcohol. Any suitable polyhydric alcohol may be used such as thosedisclosed above for use in the preparation of the hydroxyl polyesters.Any suitable alkylene oxide may be used such as, for example, ethyleneoxide, propylene oxide, butylene oxide, amylene oxide, and the like. Ofcourse, the polyhydric polyalkylene ethers can be prepared from otherstarting materials such as, for example, tetrahydrofuran, epihalohydrinssuch as, for example, epichlorohydrin and the like as well as aralkyleneoxides such as, for example, styrene oxide and the like. The polyhydricpolyalkylene others may have either primary or secondary hydroxyl groupsand preferably are polyhydric polyalkylene ethers prepared from alkyleneoxides having from two to five carbon atoms such as, for example,polyethylene ether glycols, polypropylene ether glycols, polybutyleneether glycols and the like. It is often advantageous to employ sometrihydric or higher polyhydric alcohols such as glycerine,trimethylolpropane, pentaerythritol and the like in the preparation ofthe polyhydric polyalkylene ethers so that some branching exists in theproduct. Generally speaking, it is advantageous to condense from aboutto about 30 moles of alkylene oxide per functional group of thetrihydric or higher polyhydric alcohol. The polyhydric polyalkyleneethers may be prepared by any known process such as, for example, theprocess disclosed in 1859 by Wurtz and in Encyclopedia of ChemicalTechnology, volume 7, pages 257 to 262, published by IntersciencePublishers, Inc. (1951), or in US. Pat. 1,922,459.

Any suitable polyhydric polythioether may be used such as, for example,the condensation product of thiodiglycol or the reaction product of apolyhydric alcohol such as is disclosed above for the preparation of thehydroxyl polyesters with any other suitable thioether glycol. Othersuitable polyhydric polythioethers are disclosed in U.S. Pats. 2,862,972and 2,900,368.

Any suitable polyhydric alcohol may be used as the active hydrogencontaining compound such as, for example, alkane diols such as, forexample, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,1,4-butylene glycol, 1,3-butylene glycol, 1,5-pentanediol,1,4-butanediol, 1,3-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 2,2-dimethyl-l,3-propanediol, 1,8-octanediol and the like including1,20-eicosanediol and the like; alkene diols such as, for example,2-butene-1,4-diol, 2-pentene-l,5-diol, 2- hexene-l,6-diol,2-heptene-1,7-diol and the like; alkyne diols such as, for example,2-rbutyne-1,4-diol, 1,5-hexadyne-1,6-diol and the like; alkane triolssuch as, for example, 1,3,6-hexanetriol, 1,3,7-heptane triol,1,4,8-0ctane triol, 1,6,12-dodecane triol and the like; alkene triolssuch as 4-hexene1,3,6-triol and the like; alkyne triols such as2-hexyne-1,4,6-triol and the like; alkane tetrols such as, for example,1,2,5,6-hexane tetrol and the like; alkene tetrols such as, for example,3-heptene-1,2,6,7-tetrol and the like; alkyne tetrols such as, forexample, 4-octyne- 1,2,7,8-tetrol and the like.

Any suitable aliphatic thiol including alkane thiols containing two ormore -SH groups may be used such as, for example, 1,2-ethane dithiol,1,2-propane dithiol, 1,3-propane dithiol, 1,6-hexane dithiol,1,3,6-hexane trithiol and the like; alkene thiols such as for example,

2-butene-1,4-dithiol and the. like; alkyne thiolssuch as, for example,3-hexyne-1,6-dithiol and the like.

Any suitable polyamine may be used including, for example, aromaticpolyamines such, as, for example, pamino aniline, 1,5-diarnino'naphthalene, 2,4-diaminotoluene, 1,3,5-benzene triamine, 1,2,3-benzenetriamine, l,4,5,8-naphthalene tetramine and the like; aliphaticpolyamines such as, for example, ethylenediamine, 1,3-propylenediamine,1,4-butylenediamine, 1,3-butylenediamine, diethylenetriamine,triethylenetetramide, 1,3,6-hexane-triamine, l,3,5,7-heptane tetramineand the like; heterocyclic polyamines such as, for example, 2,6-diaminopyridine, 2,4-diamino-5-aminomethyl pyrimidine, 2,5-diamino-l',3,4-thiadiazole, piperazine and the like. l

'One especially preferred group of amines useful for preparing polymersare polyamines having the primary amine groups thereof blocked byketimine or aldimine groups. The reaction of carbonyl compounds with theprimary amine groups can be illustrated as follows:

A N: C:

The useful carbonyl compounds may have the following theoreticalstructural formula where R and R are organic radicals, are eachsubstantially inert to the ketimine or aldimine formation reaction andare preferably hydrogen or short chain alkyl groups (1 to 4 carbonatoms). Preferred compounds are low molecular weight (C -C aldehydes orketones that are volatile so that an unreacted excess thereof may easilybe removed by conventional distillation practices when the reaction iscompleted. Such volatile compounds are also preferred so that when theblocked polyamine is mixed with the diisocyanate and exposed tomoisture, the freed aldehyde or ketone can be easily removed from thereaction mixture. Examples of preferred carbonyl compounds include suchaldehydes and ketones as acetone, methyl ethyl ketone, methyl n-butylketone, methyl tert-butyl ketone, ethyl isopropyl ketone, acetaldehyde,propionaldehyde, butyraldehyde, isobutyraldehyde, and the like (i.e.including hexanone and hexanal). The polyamines to be blocked preferablyhave the structure where R is a difunctional aliphatic group containingfrom 2-48 carbon atoms, R is an aliphatic group containing 1-24 carbonatoms and n is an integer of from 0-20. Reprepresentative R radicals aremethyl, propyl, butyl, decyl, hexadecyl, hexenyl, octenyl, tridecenyl,octadecyl, undecynyl and the like. Inert or non-interfering groupssuchas Cl, nitro and the like may be present on R and/or R Any suitablereaction product of a phenol with an alkylene oxide yielding a'compoundcontaining active hydrogens may be used such as, for example, thosedisclosed in US. Pat. 2,843,568, such as for example, the reactionproduct of hydroquinone with ethylene oxideto give a polyalkylenearylene ether glycol 'having a molecular weight above about 750 or otherpolyalkylene arylene ether glycols disclosed in said'patent. d

Any suitable reaction product of a phenol-aldehyde resin with analkylene oxide may be used such as, for ex ample, a novolac having theformula wherein n is 1 to Sand R is a lower alkyl radical such asmethyl, ethyl, propyl, butyl, tertiary butyl and the like reacted! with:analkylene oxide such-as those disclosed above for the preparation ofthe polyhydric polyalkylene ethers;

Any suitable reaction product of an amine with an alkylene oxide may beused such as, for example, the reaction product of an alkylene oxidewith a tolylenediamine such as, -2,4-atolylenediamine,2,6-tolylenediarnine or the like, a-diphenylmethane diamine such as4,4-diaminodiphenylmethane or the like, xylylene diamine, as well asalkylene diamines such as, for example, ethylenediamine,propylenediamine, 1,4-b'utylenediamine, hexamethylenediamine and thelike including 1,10-dodecane diamine.

Any suitable phenol may be used such as, for example,2,2-bis(p-hydroxyphenyl)propane (bisphenol A) and the like. r

Any suitable polyamide may be used such as, for example, thoseobtained'by reacting adipic acid with hexamethylenediamine and the like.

Any suitable polyacetal may be used such as, for eX- ample, the reactionproduct of formaldehyde or other suitable aldehydes with a polyhydricalcohol such as those disclosed above for use in the preparation of thehydroxyl polyester. I

Other alcohol compounds which do not necessarily fit within any of thepreviously set forth classes of compounds and which-nevertheless containactive hydrogen containing groupswhich are quite suitable for theproduction of the polymers are pentaerythritol, sorbitol,triethanolamine, mannitol,N,N,N,N-tetrakis(Z-hydroxypropyl)ethylenediamine, as well as compoundsof any of the classes set forth above which are substituted with halogensuch as, for example, chloro, iodo, bromo and the like; nitro; alkoxy,such as, for example, methoxy, ethoxy, propoxy, 'butoxy and the like;carboalkoxy such as for example, carbomethoxy, carboethoxy and the like;dialkyl amino such as, for example, dimethylamino, diethylamino,dipropylamino, methylethylamino and the like; mercapto, carbonyl,thiocarbonyl, phosphoryl, phosphato and the like.

Other substances which can be used include nature substances such ascastor oil and the like.

The molar proportions of the diisocyanate and the compounds bearingZerewitinolf active hydrogen atoms can vary widely. Those skilled in theart can determine the proportions of reactants best suited for aparticular purpose. For example, when making polyurethane elastomers,one often uses approximately equimolar amounts of glycol and thediisocyanate. Preferably, the active hydrogen containing compound willbe used in a molar ratio to the diisocyanate of 1:10 to 10:1.

The polymers can be prepared by reacting the diisocyanate and the activehydrogen containing compound at subatmospheric, atmospheric orsuperatmospheric pressure. Atmospheric pressure is preferred. Thereaction can be operated over a wide range of temperatures. Thoseskilled in the art will recognize that there are great differences inthe relative reactivity of various groups containing active hydrogenatoms, amines reacting faster than alcohols, primary alcohols reactingfaster than tertiary alcoholsto name a few examples; accordingly, onewill select a temperature at which the reaction occurs at a rateconvenient for the purpose at hand. Preferably, the reaction temperatureranges between about 20 C. and 150 C. However, the temprature is notcritical.

If desired, the reaction may be carried out in an inert solvent.Representative solvents include tetrahydrofuran, o-dichlorobenzene,chlorobenzene, xylene, methyl isobutyl ketone, toluene and ethylacetate. In general, the solvent should be free fromisocyanate-reactable groups such as groups bearing Zerewitinoff-activehydrogen atoms.

In the preparation of the polymers, a portion of the diisocyanates (i.e.up to about 90 mole percent and preferably from to 50 mole percent canbe replaced by known polyisocyanates. Representative of such knownpolyisocyanates are ethylenediisocyanate, hexamethylenediisocyanate,butylene-l,3-diisocyanate, ethylidene diisocyanate, butylidenediisocyanate, 1,2,4-butanetriisocyanate, 1,3,S-pentanetriisocyanate, pphenylene-2,2'-bis(ethylisocyanate), 1,4-naphthalene 2,2bis(ethylisocyanate), 5- chloro phenylene-1,3-bis(propyl 3 isocyanate),tolylene diisocyanate, m-phenylene diisocyanate, p-phenylenediisocyanate, diphenylene 4,4 diisocyanate, xylylene-1,4- diisocyanate,4,4 diphenylenemethanediisocyan'ate and the like. A particularlydesirable group of polyisocyanates to be employed in combination withthe instant diisocyanates in the preparation of the polymers are thosedescribed in the application of Rogier and Kama], Ser. No. 250,211,filed Jan. 9, 1963, entitled Polyisocyanates and Derivatives, now Pat.3,455,883. These polyisocyanates are derived from polymeric fat acidsand have the following idealized structural formula:

where y is 0 to 1, x is an integer of 2 to about 4 and R is thehydrocarbon group of polymeric fat acids. Preferably, x is 2. Thepolyisocyanates of the above formula wherein y is 0 are prepared byconverting the polymeric fat acids to the corresponding polymeric acidchlorides, reacting the acid chlorides with a metal azide to form thepolymeric acyl azides and then heating the acyl azides to produce thepolyisocyanates. The polyisocyanates wherein y is 1 are prepared byconverting the polymeric fat acids to the corresponding polynitriles andthen hydrogenating the polynitriles in the presence of ammonia and acatalyst such as Raney nickel to form polyamines. The polyamines arethen reacted with phosgene to give the polyisocyanates.

The following examples illustrate the preparation of polymers. The saidexamples are not to be considered as limiting.

EXAMPLE I A mixture of 2.00 g. of the ether carbonate diisocyanate asprepared in Example E and 0.48 g. of the diketimine of diethylenetriamine and methylisobutyl ketone was spread on glass with a 3-mildrawdown bar. The film became tack-free in about 3 /2 hours at 73 F. and43% relative humidity. The coating was of good appearance.

EXAMPLES K, L and M Coatings are prepared as in Example I using thediisocyanates of Examples F, G and H. Similar results are obtained.Where desired, elevated temperatures and/or catalysts such as dibutyltin dilaurate can be used to accelerate the cure of the polymers.

It is to be understood that changes and variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A dinitrile selected from the group consisting of compounds havingthe formulae:

-w a g-w OR H H on

HOR

2. The dinitrile of claim 1 wherein the sum of n and m is 15.

3. The dinitrile of claim 1 wherein R contains 1 to about 20 carbonatoms. 5 4. The dinitrile of claim 1 wherein the sum of n and m is 15and R contains 1 to about 20 carbon atoms.

5. The dinitrile of claim 1 wherein n is 8 and m is 7. 6. The dinitrileof claim 1 wherein R is a saturated aliphatic radical of 1 to about 18carbon atoms. 10 7. The dinitrile of claim 5 wherein R is methyl.

8. The dinitrile of claim 2 wherein R is 2( z)e s 9. The dinitrile ofclaim 2 wherein R is 10. The dinitrile of claim 2 wherein R is phenyl.

References Cited UNITED STATES PATENTS 2,755,264 7/1956 Riedeman 26030.4

and mixtures thereof where n is 4 to 19, m is 0 to 15, the LEWIS GOTTS,Primary Examiner sum of n and m is 13 to 19 and R is a monovalent hy- At E drocarbon radical selected from the group consisting of RIVERS 5818am Xammer saturated aliphatic, phenyl, alkyl substituted phenyl,cycloaliphatic, alkyl substituted cycloaliphatic and 'aryl sub- U.S. Cl.X.R.

substituted alkyl radicals which may contain inert substit- 26013 TN, 47CB, 47 Q, 67

uents 77.5 AP, 77.5 AT, 465.6

